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温度对酶促聚对苯二甲酸乙二醇酯降解的影响分析
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作者 伊科拉木·艾克然木 曹宇飞 +4 位作者 邢皓 丁于敬 罗宇政 韦韧 张一飞 《Chinese Journal of Catalysis》 SCIE CAS CSCD 2024年第5期284-293,共10页
近年来,聚对苯二甲酸乙二酯(PET)的酶法降解及循环利用备受关注.PET的酶法降解是在不可溶聚合物表面发生的界面催化过程,酶通过水解PET聚合物表面上可及的酯键,将聚合物逐渐分解成单体.反应温度可以从酶的催化活性、热稳定性以及PET材... 近年来,聚对苯二甲酸乙二酯(PET)的酶法降解及循环利用备受关注.PET的酶法降解是在不可溶聚合物表面发生的界面催化过程,酶通过水解PET聚合物表面上可及的酯键,将聚合物逐渐分解成单体.反应温度可以从酶的催化活性、热稳定性以及PET材料的生物可降解性等多个方面影响PET的降解过程,是影响PET酶法降解效果的主要因素之一.深入了解温度对PET酶降解过程的热力学和动力学调控机制,对PET降解酶的发掘与改造和酶法降解工艺的优化具有重要意义.本文以叶枝堆肥角质酶(LCC)的突变体WCCG为例,详细研究了温度对WCCG降解低结晶度PET(结晶度7.6%)和高结晶度(结晶度30%)PET微颗粒的影响.通常认为PET的酶促降解需要在其玻璃化转变温度(Tg,~70℃)附近或以上进行.实验测定了不同温度下的降解速率,并利用阿伦尼乌斯公式作图.结果表明,当反应温度在45℃(低于通常认为的Tg,b值约20℃)附近时,反应活化能突然降低,说明此时PET微颗粒表面的玻璃化转变已经开始,酶促降解已经能够有效进行,表现出酶解PET的界面催化特征.当温度高于75℃时,PET降解速率迅速降低,酶受热失活.研究还发现,WCCG存在热激活现象:通过将WCCG在不同温度下温育一段时间后在60℃下进行活性测定,WCCG在50-70℃范围内温育后活性显著提高;在70℃下温育4 h后其降解低结晶度PET的活性提高约1倍,同时对小分子底物4-硝基苯酚丁酯的活性也有明显提高.利用圆二色光谱和荧光光谱检测了WCCG的二级和三级结构变化.结果表明,热处理后的WCCG中的α-螺旋含量显著减少而β折叠含量增加,酶分子疏水性提高,这与分子动力学模拟结果一致.单分子力谱测试结果表明,热处理后的WCCG较处理前的酶与PET薄膜之间的粘附力从88 pN提高到150 pN.因此,WCCG的热激活是其本征催化活性改善和酶与PET表面吸附力增强共同作用的结果.WCCG在高结晶度PET的降解中也存在类似热激活现象.此外,在长时间的降解反应中,无定形区域的PET链段在相对较高的降解温度下逐渐进一步结晶,导致酶催化降解速率随着降解时间的延长而下降.综上所述,温度对酶催化PET降解过程的主要影响包括:PET表面的玻璃化转变、酶的热激活、酶的热失活、温度导致的PET材料再结晶,这些因素相互交织,说明酶促PET降解的温度依赖的复杂性.未来的研究除了继续挖掘和设计高活性、高稳定的PET水解酶外,还应提高酶在45到70℃范围内的催化活性并关注降解工艺的优化. 展开更多
关键词 聚对苯二甲酸乙二酯 酶法降解 酶的热激活 活化能 表面玻璃化转变
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酶-金属单原子复合催化剂在一锅法生物-化学反应的应用
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作者 黎晓阳 曹宇飞 +5 位作者 熊佳容 李隽 肖海 李昕阳 苟清强 戈钧 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2023年第1期139-145,共7页
酶催化与金属单原子催化结合,理论上可开发众多新的绿色化学合成反应,是催化科学的一个重要研究前沿方向.酶-金属单原子复合催化剂兼具酶和金属单原子催化剂的高效、高立体选择性等优点.目前已成功构建的单原子分散金属催化剂的载体一... 酶催化与金属单原子催化结合,理论上可开发众多新的绿色化学合成反应,是催化科学的一个重要研究前沿方向.酶-金属单原子复合催化剂兼具酶和金属单原子催化剂的高效、高立体选择性等优点.目前已成功构建的单原子分散金属催化剂的载体一般为刚性的无机载体,利用柔性蛋白分子作为载体制备单原子分散金属催化剂的技术瓶颈问题在于蛋白分子具有柔性、构象易变的特点,并且氨基酸残基与金属原子之间的相互作用力较弱,蛋白分子表面的氨基酸残基难以与金属单原子稳定结合.针对这样一个关键技术瓶颈问题,我们建立了酶-金属单原子复合催化剂的光化学合成方法.本文研究酶-金属单原子复合催化剂在生物-化学一锅级联反应合成联苯类手性醇中的催化性能.联苯类手性醇是手性药物的重要中间体,通常通过多步化学法或生物-化学级联法制备.相比于多步化学法,利用生物-化学级联反应制备联苯类手性化合物具有反应条件温和、选择性高、环境友好等优点.采用光化学法合成脂肪酶-钯单原子复合催化剂(Pd_(1)/CALB-Pluronic),通过球差矫正扫描透射电镜和扩展X射线吸收精细结构表征复合催化剂的形貌.首先研究了Pd_(1)/CALB-Pluronic复合催化剂中单原子分散Pd催化的C-C偶联反应催化效率,然后考察了它在生物-化学一锅级联反应中的催化性能;发现该催化剂在C-C偶联反应中具有比常用的Pd均相催化剂和Pd非均相催化剂更好的活性.在碘苯和苯乙炔的Sonogashira反应中,Pd_(1)/CALB-Pluronic的TOF值大于均相催化剂Pd(PPh3)4,是多相商业催化剂Pd/C的3.5倍.Pd_(1)/CALB-Pluronic重复使用10次后,活性仍保留97%,具有很好的稳定性.通过DFT计算分析催化反应路径,提出了Pd_(1)/CALB-Pluronic复合催化剂的2价Pd单原子在Sonogashira反应中可能存在Pd^(Ⅱ)/Pd^(Ⅳ)催化机理.本文开发了(R)-1-(4-联苯)乙醇的生物-化学一锅级联反应合成新路线:Pd_(1)/CALB-Pluronic复合催化剂在30℃的水溶液中催化(±)-1-(4-溴苯基)乙酸乙酯和苯硼酸反应生成(R)-1-(4-联苯)乙醇.在该过程中,CALB催化的立体选择性水解反应和Pd单原子催化的C-C偶联反应同时进行.其中,CALB催化(±)-1-(4-溴苯基)乙酸乙酯中的R型异构体水解为(R)-1-(4-溴苯基)乙醇,Pd单原子催化(R)-1-(4-溴苯基)乙醇与苯硼酸进行Suzuki反应生成(R)-1-(4-联苯)乙醇.Pd_(1)/CALB-Pluronic复合催化剂在30 oC下催化生物-化学一锅级联反应合成(R)-1-(4-联苯)乙醇,其催化效率是商业催化剂Pd/C和CALB-Pluronic催化剂组合的31.3倍. 展开更多
关键词 化学-酶催化反应 酶-金属复合催化剂 单原子催化剂 协同催化 手性醇
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Hybrid enzyme catalysts synthesized by a de novo approach for expanding biocatalysis 被引量:3
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作者 yufei cao Jun Ge 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2021年第10期1625-1633,共9页
The two major challenges in industrial enzymatic catalysis are the limited number of chemical reaction types that are catalyzed by enzymes and the instability of enzymes under harsh conditions in industrial catalysis.... The two major challenges in industrial enzymatic catalysis are the limited number of chemical reaction types that are catalyzed by enzymes and the instability of enzymes under harsh conditions in industrial catalysis.Expanding enzyme catalysis to a larger substrate scope and greater variety of chemical reactions and tuning the microenvironment surrounding enzyme molecules to achieve high enzyme performance are urgently needed.In this account,we focus on our efforts using the de novo approach to synthesis hybrid enzyme catalysts that can address these two challenges and the structure-function relationship is discussed to reveal the principles of designing hybrid enzyme catalysts.We hope that this account will promote further efforts toward fundamental research and wide applications of designed enzyme hybrid catalysts for expanding biocatalysis. 展开更多
关键词 Expanding biocatalysis In situ synthesis Hybrid enzyme catalysts Structure-function relationship Rational design
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Research on keystone formatting based on non-baseband interpolation 被引量:3
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作者 yufei cao Xiaoguang Qu Peikang Huang 《Journal of Systems Engineering and Electronics》 SCIE EI CSCD 2010年第4期562-565,共4页
When there is Doppler ambiguity number mutation,keystone formatting is no longer valid because of integration performance deterioration and false velocity estimation.A novel keystone formatting method based on non-bas... When there is Doppler ambiguity number mutation,keystone formatting is no longer valid because of integration performance deterioration and false velocity estimation.A novel keystone formatting method based on non-baseband interpolation is presented.It has a different half blind velocity range comparing with normal keystone formatting.Furthermore,there is non-superposition between half-blind-velocity-range of keystone formatting based on baseband and that of non-baseband interpolation.So a synthesizing keystone formatting is proposed to avoid the half-blind-velocity effect.Simulation results of the proposed method show that integration deterioration and velocity estimation falsity can be eliminated effectively. 展开更多
关键词 keystone formatting half-blind-velocity coherent integration velocity estimation.
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A Caching Scheme for Session Setup in IMS Network
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作者 yufei cao Jianxin LIAO +1 位作者 QI QI Xiaomin ZHU 《Wireless Sensor Network》 2009年第3期132-141,共10页
In IP Multimedia Subsystem (IMS), the session setup delay is a critical value for Quality of Service (QoS). The existing approaches to improve this metric depend on optimization of Session Initiation Protocol (SIP) me... In IP Multimedia Subsystem (IMS), the session setup delay is a critical value for Quality of Service (QoS). The existing approaches to improve this metric depend on optimization of Session Initiation Protocol (SIP) message transmitting and signaling flows. Unfortunately, some service features are missing considered al-though they have been used widely in traditional 2G networks. This paper proposes a novel session setup scheme based on caching, upon the investigation of the performance of IMS session establishment. This mechanism involves cache based local routing policy and an adaptive caching algorithm, which can decrease call setup delay effectively as cached information in the terminating Serving-Call Session Control Function (S-CSCF) hit. The analytical model is deduced, as well as the delay and cost ratio functions are presented based on the model. Moreover, the analytical model is validated through the performance simulation in which the performance of the proposed novel method is evaluated against the basic session setup mechanism in terms of cost and delay. 展开更多
关键词 SIP SESSION CACHING IMS
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